BS PD CEN TR 15160-2005 Petroleum and related products - Applicability of diesel fuel test methods for Fatty Acid Methyl Esters (FAME) - Information and results non round robin tes.pdf

1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58fuel test methods for Fatty Acid Methyl Esters (FAME) Information and results on round robin testsI

2、CS 75.160.20Petroleum and related products Applicability of diesel PUBLISHED DOCUMENTPD CEN/TR 15160:2005PD CEN/TR 15160:2005This Published Document was published under the authority of the Standards Policy and Strategy Committee on 12 December 2005 BSI 12 December 2005ISBN 0 580 47336 8The British

3、Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online.

4、This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Compliance with a Published Document does not of itself confer immunity from legal obligations.Summary of pagesThis document comprises a front cover, an inside f

5、ront cover, the CEN/TR title page, pages 2 to 42, an inside back cover and a back cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued since publicationAmd. No. Date Commentsenquiries on the interpretation, or proposals for change, a

6、nd keep UK interests informed; monitor related international and European developments and promulgate them in the UK.A list of organizations represented on this committee can be obtained on request to its secretary.Cross-referencesNational forewordThis Published Document is the official English lang

7、uage version of CEN/TR 15160:2005.The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European committee any TECHNICAL R

8、EPORTRAPPORT TECHNIQUETECHNISCHER BERICHTCEN/TR 15160August 2005ICS 75.160.20English VersionPetroleum and related products - Applicability of diesel fuel testmethods for Fatty Acid Methyl Esters (FAME) - Information andresults on round robin testsProduits ptroliers et produits reli - Application des

9、mthodes dexamination de gazole en Methyl Acides Graz(UMAG) - Information t rsultats dexamination inter-laboratoirMinerallerzeugnisse und verwandte Produkte -Anwendbarkeit von Prfverfahren fr Diesel-Kraftstoffe aufFettsure-Methylester (FAME) - Informationen undErgebnisse aus RingversuchenThis Technic

10、al Report was approved by CEN on 18 June 2005. It has been drawn up by the Technical Committee CEN/TC 19.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,

11、Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2005 CEN All rights of e

12、xploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CEN/TR 15160:2005: E2 Contents Page Foreword 3 Introduction4 1 Summary5 2 Background.5 3 Basis of the work 6 4 Details of the round robin.7 5 Results.7 6 Conclusion 10 Annex A (informative) List of participa

13、nts in working group 26 activities .11 Annex B (informative) Report of the result of the round robin on determination of flash point using the rapid equilibrium close cup method (prEN ISO/DIS 3679)13 Annex C (informative) Report of the result of the round robin series on distillation of petroleum pr

14、oducts at reduced pressure (ASTM D 1160).20 Annex D (informative) Preliminary study on applicability of distillation of petroleum products at atmospheric pressure (EN ISO 3405) on blends of FAME in diesel fuel25 Annex E (informative) Report of the results of the round robin on determination of carbo

15、n residue via the micro method (EN ISO 10370).29 Annex F (informative) Report of the result of the round robin series on corrosiveness to copper via the copper strip test (EN ISO 2160).33 Annex G (informative) Report of the result of the round robin series on determination of fatty acid methyl ester

16、s (FAME) in middle distillates via infrared spectroscopy (prEN 14078)36 Annex H (informative) Influence of FAME origin on the measure of FAME content in mineral oil using prEN 14078 (Determination of fatty acid methyl esters (FAME) in middle distillates via infrared spectroscopy method).40 CEN/TR 15

17、160:20053Foreword This document (CEN/TR 15160:2005) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat of which is held by NEN. This document has been prepared under a mandate g

18、iven to CEN by the European Commission and the European Free Trade Association. CEN/TR 15160:20054 Introduction This Technical Report gives the results of the round robin series of tests to evaluate different test methods on their compatibility on FAME which are referred to in: EN 14213: Heating fue

19、ls Fatty acid methyl esters (FAME) Requirements and test methods, and EN 14214: Automotive fuels Fatty acid methyl esters (FAME) for diesel engines Requirements and test methods. CEN/TC 19 acknowledges Mrs. M.F. Benassy from Total, all project leaders of each test method as indicated in the annexes

20、and all other participants in CEN/TC 19/WG 26 “FAME related fuel test methods“ (see Annex A) for their contribution to this report. CEN/TR 15160:200551 Summary One task under the European Mandate M/245 was to investigate the applicability of existing petroleum test method standards for fatty acid me

21、thyl esters (FAME). For this task CEN/TC 19 has founded a separate working group 26, which has validated 24 methods via round robins, including the development of new test methods. The work of CEN/TC 19/WG 26 was aimed at the drafting of amendments for existing ISO standards (with test methods for f

22、ossil fuels). These amendments include the extension of the scope of the standards to biodiesel as well as the new precision data for biodiesel. To get these new precision data (repeatability NOTE The flash point for fatty acid methyl esters is high ( 160 C). Methanol is used for the manufacturing o

23、f FAME. Methanol is to a large extent removed from the final product, but remnants may still be present. The current specification for 100 % FAME allows 0,2 % (m/m) methanol max. Methanol as such has a flash point of 11 C. The use of non-equilibrium test methods for the determination of flash point

24、for products containing trace amounts of highly flammable material (i.e. like FAME containing methanol) give poor repeatable test results due to i) non homogeneous heat transfer conditions, and ii) unfavourable V/L (Vapour/Liquid) conditions in the test cup. 2) optical detection is unsuitable, becau

25、se methanol burns (and flashes) with a colourless, invisible flame. NOTE The flash point of FAME is caused by methanol, which gives a colourless, invisible flame. Even experienced operators have difficulties to detect this flame using their eyes. 4 At the date of publication of this document a revis

26、ion (EN ISO 2719) has been published in November 2002. CEN/TR 15160:200514 Both procedures A and B of EN 22719 were tested (see Table B.1). Procedure A gave repeatable results for FAME A, giving a greenish flame, caused by the FAME itself, i.e. all methanol is evaporated during the test without givi

27、ng a flash. Procedure A gave poorly repeatable results for FAME B. Procedure B gave poorly repeatable results for FAME A and B. These results clearly demonstrated that EN 22719 is not applicable for 100 % FAME. Based on the above, the most suitable test method is an equilibrium test method with a ma

28、ndatory non-optical flash detection. According to state of the art, EN ISO 3679 test method was considered to be most appropriate to run a round robin with. Table B.1 Flash point determinations of 100 % FAME by EN 22719 FAME A FAME B Procedure A Procedure B Procedure A Procedure B 166 (134 a) 160 (1

29、18 b) 126 116 166 (132 a) 154 (122 a) 126 120 168 (120b) 156 (118 b) 124 122 (122b) 160 (126a) 128 124 140 130 34 134 148 avery weak flash observed, flame blown out, no flame observed bflame blown out (sucked into the cup) B.4 Pre-study for round robin with prEN ISO/DIS 3679 B.4.1 Set-up The suitabi

30、lity of prEN ISO/DIS 3679 was initially tested at SRTCA. For this purpose a flash point tester was got on loan. The first tests showed that repeatable flashpoints results for FAME, containing methanol at several concentrations, can be achieved using this apparatus (see Figure B.1, flash point App. 1

31、, 2 ml). Therefore SRTCA decided to get possession of such a flash point tester. The samples, tested on apparatus 1, were also tested on this new apparatus (see Figure B.1, flash point App. 2, 2 ml). It was noted that the flashpoints were somewhat lower on apparatus 2. The curve through the flashpoi

32、nts is S-shaped; the left end site is limited by the flash point of FAME without methanol, the right end site is asymptotically limited by the flash point of methanol, the steep middle of the curve is around the methanol concentration of 0,2 % (m/m) (i.e. the current FAME specification). According t

33、o prEN ISO/DIS 3679, a specified volume is introduced into the test cup, which is maintained at the temperature of the estimated flash point of the material under test. After a specified time, a test flame is applied and the presence or absence of a flash observed. For flashpoints up to and includin

34、g 100 C, the specified test portion is 2 ml and the specified time is 1 minute; for flashpoints above 100 C the specified test portion is 4 ml and the specified time is 2 min. When 4 ml FAME is introduced instead of 2 ml, then much lower flashpoints are achieved (see Figure B.1, flash point, App. 2,

35、 4 ml). Clearly the two curves through the flashpoints derived by 2 ml and 4 ml do not overlap, which is partly accounted for by differences in V/L (Vapour/Liquid) ratios: V/L for 2 ml and 4 ml test portions are 9/1 and 8/2 respectively. It was noted that the flashpoint results for 100 % FAME withou

36、t methanol and 100 % FAME with methanol 0,5 % (m/m) were less sensitive to sample volume. Generally the flashpoints for 100 % FAME will be above 100 C, so a test portion of 4 ml is required. However, for samples containing more than ca. 0,17 % (m/m) methanol, the flashpoint will be 100 C will be exp

37、ected when using a 2 ml test portion, so a 4 ml test portion is required, etc. CEN/TR 15160:200515Obviously the test method cannot be used for FAME samples regarding the specified test portion. Hereto the test method had to be modified, i.e. specifying a single test portion for FAME samples, irrespe

38、ctive of flashpoint. The fixation of the test portion to either 2 ml or 4 ml was up for debate. CEN/TR 15160:2005pEffect ofmethanol content,apparatus andsample intake on FP5055606570758085909510010511011512012513013514014515015516016517017518018500,050,10,150,20,250,30,350,40,450,50,55Methanol, %m/m

39、Flash point, CFlash pointApp.1,2mlFlash pointApp.2,2mlFlash pointApp.2,4mlFlash pointApp.1,2mlP.M.-checkISO3679ISO2719Apparatus1Apparatus2Figure B.1 EN ISO3679 at 100 %FAMECEN/TR 15160:200516 17 B.4.2 2 ml test portion pro: the flashpoint limit for transportation regulation is around 65 C, which is

40、based on 2 ml sample intake contra: flashpoint for 100 % FAME will generally be 110 C, so test method is not performed accordingly B.4.3 4 ml test portion pro: flashpoint for 100 % FAME will generally be 100 C, so the original test method is performed accordingly most of the time. contra: 1) for sam

41、ples containing ca. 0,17 % (m/m) methanol, flashpoint will be 70 C) for flashpoints up to 150 C but is similar to the repeatability stated in prEN ISO/DIS 3679 at higher flashpoints. The reproducibility (R), however, cannot be considered as constant: it varies between 10 C and 20 C, except for one h

42、igh-flyer at 26 C. The reproducibilities found for this round robin are significantly higher than the reproducibilities stated in prEN ISO/DIS 3679 (i.e. 0,083 X0,9 for flashpoints 70 C). The R is maximal around the 0,2 % (m/m) methanol concentration (samples 4 and 9) and decreases (significantly) g

43、oing to higher and lower concentrations. So there clearly is a relationship of R and the methanol (flashpoint) concentration. However, the standard software is not able to linearise this (Gaussian) relationship and consequently estimates the global reproducibility to 15,8 C. This implies that the re

44、producibility is significantly underestimated at the flash point specification (i.e. flashpoint at 0,2 % (m/m) methanol) and is significantly overestimated at higher or lower methanol concentrations. Based on the physics involved one might expect that this type of error distribution is not that exce

45、ptional and will occur more frequently, certainly for any flash point caused by “trace contamination“ (mixing a high flash point material with trace amounts of low flash material). And it is exactly this situation, which has the most potential hazard in terms of flammability. This issue has been add

46、ressed to the standardization bodies (i.e. ASTM and ISO TC 28 / TC 35). B.8 Conclusion prEN ISO/DIS 3679 and its later successor, the test method for the determination of flashpoint, is applicable for 100 % FAME, when the following modifications are implemented: 1) For FAME samples, 2 ml test portio

47、n and 1 min stabilisation time are dictated. 2) The use of the flash point detector is mandatory for testing FAME samples. The repeatability derived for the round robin can be regarded as similar to the methods repeatability. The derived reproducibility, however, was significantly higher than the me

48、thods reproducibility. CEN/TR 15160:200520 Annex C (informative) Report of the result of the round robin series on distillation of petroleum products at reduced pressure (ASTM D 1160) C.1 Scope In this round robin the applicability of test method ASTM D 1160 “Distillation of Petroleum Products at Re

49、duced Pressure“ towards FAME as 100 % diesel fuel is investigated. The repeatability and reproducibility are determined if the test method was applicable. NOTE This study has been supervised by Mr. M.L. Daane. C.2 Assessed standard documents EN ISO 3170:1998, Petroleum liquids Manual sampling (ISO 3170:1988) EN ISO 4259:1995, Petroleum products Determination and application of precision data in relation to methods of test (ISO 4259:1992/Cor.1:1993) ASTM D1160 :95, Distillatio